A procedure was developed for the determination of several barbiturates, amobarbital, barbital, hexobarbital, and secobarbital, using a C18 column (120 x 4.6mm) and micellar liquid chromatography (MLC) mobile phases containing sodium dodecyl sulfate (SDS) and propanol, butanol, or pentanol as a modifier, with UV detection at 230 nm. After the application of an interpretative strategy of optimization, the four barbiturates can be resolved and determined in serum samples, allowing the direct injection in 0.10 M SDS-4% (v/v) butanol, pH 7, with an analysis time below 8 min. In the proposed MLC procedure, linearities (r > 0.999), limits of detection (ng mL(-1)) in the 30-70 range, repeatabilities, and intermediate precision below 1.8% are adequate for the quantification. The proposed method could be applied to the determination of barbiturates in serum samples with recoveries that agreed with the concentration added. (C) 2002 Elsevier Science (USA). All rights reserved.